Polymeric organic boron-nitrogen-sulfur compounds



United States Patent 3,357,949 POLYMERIC ORGANIC BORON-NITROGEN- SULFUR COMPOUNDS Elmar-Manfred Horn, Aachen, and Hans Niederprum, Monnheim, Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a German corporation No Drawing. Filed May 1, 1964, Ser. No. 355,563 Claims priority, applicatigg (izermany, May 9, 1963,

30 Claims. Cl. 260-465) ABSTRACT OF THE DISCLOSURE Production of thermally stable polymeric organic boron-nitrogen-sulfur compounds by mixing, e.g., at 0-600" 0., a borane amine of the formula R BH in which R is primary, secondary or tertiary amine with one or more thiocyanates of the formula in which R is a hydrocarbon radical, optionally containing silicon, phosphorus, tin, oxygen, halogen and/ or nitrogen, and m is an integer from 1 to 6, and optionally with one or more nitriles of the formula in which R is a hydrocarbon radical, optionally containing halogen and/ or nitrogen.

wherein R can be a primary, secondary or tertiary amine, are reacted at temperatures between 0 C. and 600 C. with thiocyanates of the general formula R (SCN) possibly in the presence of nitriles of the general formula wherein R denotes a hydrocarbon radical which may contain silicon, phosphorus, tin and/ or oxygen atoms, R denotes a hydrocarbon radical, and m and n are integers.

It has been found that organic, organo-silicon, organophosphorus and organo-tin thiocyanates, mixtures of the said thiocyanates, and mixtures which may consist of one or more of the said thiocyanates and one or more 3,357,949. Patented Dec. 12, 1967 nitriles, can be reacted with borazanes, with splitting oif of the amine component R of the borazane and with splitting oif of hydrogen, to form high-molecular organic polymers containing boron, nitrogen and sulfur. The proportions of starting substances are preferably selected in such a manner that one mol of borazane is used per mol of thiocyanate group. When starting from thiocyanate/nitrile mixtures, one mol of borazane is preferably used for every mol of thiocyanate group as well as for every mol of nitrile group; however, the process according to the invention can also be carried out with other molar proportions of borazane and thiocyanate, or thiocyanate and nitrile. For example, when using olefinically or acetylenically unsaturated thiocyanates and/or nitriles, it is in some cases of advantage to choose a higher molecular ratio, referred to the borazane employed.

Dependent upon the conditions of production and the thiocyanates or thiocyanate/nitrile mixtures used, there are obtained resins, pastes or oils which chiefly exhibit a surprising thermal stability and can be used as plant protectives, as intermediates, as additives to motor fuels and lubricants, and for the production of polymers with neutron-absorbing properties.

For the present process, borazanes are used, the amino components of which can be primary, secondary or tertiary C -C alkyl, cycloalkyl or aryl amines, mixed alkyl-cycloalkyl-aryl amines, or possibly alkylated heterocyclic amines, preferably pyridincs and piperidines.

Because they are easily obtainable, N-triorgano-bora- Zanes are preferably used, for example, N-trirnethyl-borazane, N-triethyl-borazane, N-tripropyl-borazane, N-diethyl N-butyl-borazane, N-dimethyl-N-cyclohexyhborazane, N-dimethyl-N-phenyl-borazane or the pyridine-borine; however, other borazanes, such as e.g. N-diethylborazane or N-laurylborazane can also be used as starting substances.

Monoor polythiocyanates of the general formula can be used. In this formula m denotes an integer preferably from 1 to 6, p denotes an integer from 0 to 1. If p is 0, Z has the meaning of R R denotes alkyl, alkenyl, alkinyl, cycloalkyl or aryl groups or alkyl-, cycloalkyl-, aryl-alkoxy-, aroxy-, halogen-, primary, secondary or tertiary amine, monoor polysubstituted derivatives thereof. If p is 1, Z denotes alkylene, oxyalkylene, cycloalkylene, cyclooxyalkylene, arylene or oxyarylene groups with 1 to 6 carbon atoms. R has the meaning of or with m(ZSCN)-groups substituted disiloxane or polysiloxane groups. R denotes hydrogen, alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl aryl, alkoxy, aryloxy-groups.

When organo-silicon, organo-phosphorus or organotin monoor polythiocyanates are used, the silicon, phosphorus or tin atom in these compounds is always separated from the thiocyanate group either by at least one carbon atom, or by one oxygen atom and at least one carbon atom.

As examples of suitable monothiocyanates there may be mentioned: possibly substituted aliphatic monothiocyanates, such as methylthiocyanate, ethylthiocyanate, nand i-propylthiocyanate, n-, iand tert.-butylthiocyanate, hexylthiocyanate, octylthiocyanate, dodecylthiocyanate, hexadecylthiocyanate, octadecylthiocyanate, methoxymethylthiocyanate, 'benzylthiocyanate, 4-chloro-benzylthiocyanate, 2-fluoro-ethyl'thiocyanate, 2-brorno-l-methyl-propylthiocyanate, 5,5,5-trifluoro-pentyl-thiocyanate, 2- methyl Z-thiocyanatobutane, 3,5,5-trimethyl-hexyl-thiocyanate, allyl-thiocyanate, 3-chloro-allyl-thiocyanate, 3- ethyl-allyl-thiocyanate, oleylthiocyanate, 2-tl1iocyanatobutadiene-( 1,3); possibly nuclear-substituted cyclohexylthiocyanates, such as cyclohexylthiocyanate and 4-methylcyclohexyl-thiocyanate; possibly nuclear-substituted aromatic thiocyanates, such as phenylthiocyanate, l-naphthyl-thiocyanate, 3-methylphenyl-thiocyanate or 4-dimethylamino-phenyl-thiocyanate.

Examples of compounds with several thiocyanate groups in the molecule are:

1,4-dithiocyanto-butene-'(2), 2,3-dibromo-1,4-dithiocyanato-butane, bis(2-thiocyanto-ethoxy)-methane, di-(2,2-thiocyanto-ethyl) ether and di-(4,4-thiocyanto-n-butyl) ether.

The monoor polythiocyanates containing silicon, or silicon and oxygen are either silane derivatives, such as for example,

trimethyl-thiocyanto-methylsilane, ethyl-dimethyl-thiocyanto-methylsilane, phenyl-dimethyl-thiocyanto-methylsilane, methoxy-dirnethyl-thiocyanto-methylsilane, ethoxy-rnethyl-ethyl-thiocyanto-methylsilane, phenoxy-diphenyl-thiocyanto-methylsilane, trimethylpthiocyanto-phenyl) -si1ane, trimethyla-thiocyanto-ethyl) -si1ane, trirnethyl- (y-thiocyanto-propyl) -silane, bis-(thiocyanto-methyl -dimethylsilane, triphenyl- -thiocyanto-propyl) -silane or triethyl- (2-thiocyanto-ethoxy -silane,

or they are open-chain or cyclic poly-siloxanes which contain one or more thiocyanate groups in the end position or side position, whereby in these siloxane derivatives, as also in the above-mentioned silane derivatives, the silicon atom is always separated from the thiocyanate group by at least one carbon atom, or by one oxygen atom and at least one carbon atom. Examples of siloxane derivatives which can be used for the process according to the invention are:

1,3-bis- (thiocyanto-methyl) l 1,3,3-tetramethyldisiloxane,

heptamethyl-thiocyanto-methyl-cyclo-tertasiloxane,

trimethyl-tris- (thiocyanto-methyl) -cyclo-trisiloxane and the a,w-bis-(thiocyanto-methyl)-polymethylpolysiloxanes.

A process for the production of polymeric organic boron-nitrogen compounds has already been developed, which consists in reacting borazanes with nitriles. It has now been found that also mixtures which consist of organic, organo-silicon, -phosphorus and/ or -tin thio- 4 cyanates on the one hand and nitriles on the other hand are suitable for the reaction on which the process according to the invention is based; thereby organic monoor polycyanides of the general formula can be used, wherein R is an aliphatic, cycloalphatic or aromatic radical which may be monoor poly-substituted by alkyl, cycloalkyl, aryl, alkoxy, aroxy, primary, secondary or tertiary amino groups and/or halogen atoms, and n is an integer, preferably from 1 to 6.

Examples of monoitriles are: acetonitrile, propionitrile, butyronitrile, the nitriles of octane-, dodecaneand hexane-carboxylic acid, possibly nuclear-substituted hexahydro-benzoic acid nitriles, possibly nuclear-substituted benzonitriles (e.g. benzonitrile and Z-chloro-benzonitrile) and possibly nuclear-substituted naphthaonitriles. Examples of compounds with several nitrile groups in the molecule are: malonic acid dinitrile, glutaric acid dinitrile, adipic acid dinitrile, cyanoform and 1,1,3,3-tetracyanopropane. The organic radical containing one or more nitrile groups may moreover be saturated or aromatically, olefinically or acetylenically unsaturated.

If organic thocyanates or silicon-, phosphorusor tincontaining organic thiocyanates are used, which are olefinically or acetylenically unsaturated, and/or olefinically or acetylenically unsaturated nitriles such as allyl-thiocyanate, 2 thiocyanto butadiene-(l,3)- allyl-dimethylthiocyanathomethyl-silane, 1,4 dicyano butane (2) or l,1,2,2-tetracyanoethylene, then there usually also occurs, in addition to the reaction of the borazane with the thiocyanate group and, possibly, the reaction of the borazene with the nitrile group, a hydroboration of the double or triple bond which frequently leads to an additional crosslinking of the polymeric organic boron-nitrogen-sulfur compounds.

An additional cross-linking or the polymeric compounds according to the invention which contain boron, nitrogen, sulfur and possibly silicon, phosphorus or tin, can also be achieved by using nitriles and/ or thiocyanates which are substituted by primary or secondary amino groups. In this case an additional condensation takes place which proceeds, for example, according to the known scheme The reactions, forming the basis of the process according to the invention, of borazanes with organic, organosilicon, -phosphorus and/or -tin thiocyanates, or with mixtures consisting of the said thiocyanates and nitriles, are carried out at temperatures between 0 C. and 600 C., expediently at temperatures above C., whereby it is possible to work under normal pressure, under foreign gas pressure (e.g. under nitrogen pressure) or also under the hydrogen pressure caused by the hydrogen which is split otf during the reaction.

Apart from using, for example, olefinically or acetylenically unsaturated thiocyanates or nitriles, a further possibility of influencing the properties of the boron-nitrogensulfur compounds produced according to the invention consists in that the thiocyanate component is not employed in the form of a well-defined uniform compound but that any thiocyanate mixtures are used, possibly mixed with one or more nitriles.

The properties of the polymers produced according to the present process can also be modified to a large extent by adopting a specific procedure for their production, for example,

(1) mixing the borazane and the thiocyanate and, possibly, the nitrile and subsequently heating to the reaction temperature under normal pressure or increased pressure, or

(2) heating one of the starting products to the reaction temperature and then adding the other component or components, for example through a dropping funnel or, when working under pressure, for example by means of 6 EXAMPLE 6 115 g. (1 mol) of N-triethyl-borazane dissolved in 500 ml. of diethyl-benzene are mixed in a round flask fitted with stirrer, descending condenser, immersed a dosag? Pump or thermometer and dropping funnel, this mixture is heated (3) carrying out the reaction accordingto the methods to about C 115 (1 mol) of mbutyuhiocyanate nlennoped under (I) and (2) m an mart Solvent or are then added dropwise within about 40 minutes, and dispersing agent. For example, hydrocarbons, such as the separated triethylamine and the bulk of the diethylbenzene toluene Xylene dledlylbenzene and tmpethyl' benzene used as solvent are finally distilled off under benzene or ethers such. as dlbutyl ether and dlbenzyl 10 normal pressure. During these operations a total of 2.8 ether can used for thls P litres (measured at 205 C.) of hydrogen evolve (identi- The following examples are given for the purpose of fled gas chmmat0graphy) After removal of the lnustratmg the mVentwnresidual volatile components in a vacuum, 123 g. of a EXAMPLE 1 yellow oil are obtained, which contains 7.3% of boron, In an autoclave of 0.9 litre capacity, fitted with stirrer, gga zg g t fig g fi gf g g ig 2 1 252? of a mixture consisting of 79.5 g. (0.5 mol) of ethyl-dip D methyl-thiocyanatomethyl-silane, 57.5 g. (0.5 mol) of n =1.5280, d =l.003, 1 =26.8 cp. N'methyl'borazane and of dry benzene 1S heated and is soluble, for example, in benzene, dioxan, n-hexane, at about 200 C. for 1 /2 hours, whereby the pressure addi n buty1 ether and carbon tetrachloride. justs itself to 21.5 atmospheres. After cooling to room temperature, the final pressure amounts to 3.5 atmos- EXAMPLE 7 p The p g y p hydrogen (ldentrfied y gas To a solution of 126.5 g. 1.1 mol) of N-triethylf p y) 1S blown the Content f the borazane in 250 ml. of diethylbenzene, heated to about clave is transferred to a round flask, the triethylamme 150 (3,, are dded dropwise, in the apparatus described which has been split off and the benzene used as solvent above, Within about 15 minutes, 532 f a li are distilled oil under normal pressure, residual volatile bi -(t-hiocyanato-niethyl) poly-dimethyl-siloxane which, compounds are removed in a vacuum at temperatures of with a thiocyanate content of 9.9 percent by weight of about 130l40 C., and 86 g. of a brown-coloured oil SCN, has the approximate composition are obtained, contains bOI'OIl, Of sulfur, 9.0% of nitrogen, 15.4% of S111COI1 and 0.13% of of active hydrogen (hydridic-hydrogen, probably directly gg ff up l a linked with boron, determined gas-volumetrically by i 1 pa 6 2; i gf i hydrolysis with warm semi-concentrated sulfuric acid). ams o O @9 0 0 Sup 0 0 mm- This oil ossesses the followi h ical constants- 32'1% of slhcon and 031% of acme hydrogen 1 5 d 007 g ys d 1 b1 The oil is characterised by the following constants: 2 18 n =l.4352, d., =1.005, 1, ,.=77.9 cp. and soluble in f example benzene Carbon tetrachloride dloxan e.g. dioxan, hexane, benzene, carbon tetrachloride and didi-n-butyl ether and n-hexane. nqmtyl ethen Further reactiofls W1 1ich are carried out in an 40 Further polymers containing boron, nitrogen and Clave, 3T6 Summarlsed 111 the f011W1I1g Table Thafeln sulfur, and obtained by reaction under normal pressure %-H,, denotes content of actlve hydrogen in percent. are described in Tables 2 and 3.

TABLE 1 Starting substances Ex.

Borazane Thloeyanate Nitrile Solvent (C2H5)3N.BH3, 115 g.=1 mol CzH5SCN, 87 g.=1 mol (CQHQKNBH 60.5 g.=0.525 molt.-- i-C3H7SCN,50.5g.=0.5rnol Benzene, ml. (CQHmNBHQ, 120.5 g.=1.05 mol. H'CJHQSCN, 57.5 g.=0.5 ol Adipiedlnitrile, 27 g.=0.25 mol Diethylbenzene, 150 ml. (CQH5)3N.BH3, 158.1 g.=1} mol n-C4H9SCN, 86.3 g.=0.75 mol 1.4-dilcyan0butene-(2), 26.5 g.=0.25 Do.

Reaction Product obtained Conditions Ex. Soluble in e.g.

Time Arnoamt Appearance Analyses Physical constants 2 30 min-. 93 Grey-brown oil 9.51%}; S n =1.5031, d4 =0.980, 1fi=44.7 op-.. Dloxan, benzene, 0014.

0.22%; H.., 14.8% N. 3 1hour 160-180 44 Dark brown oil--- 10.4% B, m)"=1.5374,d =l.036 Dloxan, benzene, hexane 25.9% S, CCli. 12.9% N, 0.42% H. 4 1hour -180 98 Yellowish resin 10.8% B, Turns pale brown in closed tube at Little soluble in hot 0014.

12.0% S 400 C.; no melting or sintering up to r g, g, 525 0. 5 45 mtn 170 135 Yellow resin 10.0% 1%, l Turns pale brown in closed tube at Dioxan, benzene, dibutyl- 15.4% S, 450 0.; no melting or sinterlng up to ether, 0014. 14.3% N, 525 C. 0.21% H,

TABLE "3Continued E Reaction Conditions Product obtained Time Tergp)., Al1(10IjlIlt Appearance Analyses Physical constants Soluble 1n e.g.

12...- 40 min- 120-140 101 Yellow oil 4.9% B, 1m =1.5253 Benzene, dioxan, C14.

13. 1 hour--. 125-140 160 Yellow to orange 5.3%;18 nr =1.6061, m"=1.2003, 1m=682.3 cp Dioxan, benzene, CS2, CCl4.

14 mln. 135-175 70 Yellow resin 1333,9158 M.P.: 130 C Dioxan tetrahydroiuran.

15..-. 4 hours. up to 140 63 Yellow-orange oil 32%;,8 nD' =l.5392, dfi=1.150, 1 -=21.1 cp Dioxan, C01, 081.

EXAMPLE 16 member selected from the group consisting of hydrogen,

In the apparatus described in Example 6, a mixture of 103.5 g. (0.9 mol) of N-triethyl-borazane and 200 ml. of isopropyl-benzene is heated to about 135-140 C. while stirring, and then there are added dropwise within about 5 minutes 203 g. of a polymethyl-siloxane substituted by thiocyanato-methyl and having, with a thiocyanate content of 169 percent by weight of SCN, the,

approximate composition 3 8Si (CH O. 14 (NCS-CH Si(CH 0.2 (CH SiO in which R is a member selected'from the groupvconsisting of pyridine, alkylated pyridine, piperidine, alkylated piperidine, and primary, secondary and tertiary amines substituted with a substituent selected from the group consisting of C a1kyl, cyclohexyl, phenyl and corresponding mixtures of such substituents, with thiocyanate having the formula 3 R (ZSCN) in which m is an integer from .1 to 6 and p is an integer from 0 to 1, such that when p is 0, Z is R 'which'is a member selected from the group consisting of alkyl,

alkenyl, alkynyl, cyclohexyl, phenyl, naphthyl, and each,

such member which is substituted with a 'substituent' se-' lectedtfrom the group consisting of alkyl, phenyl, alkoxy, halo, hal oalkyl, halophenyl, alkyl substituted amino, and mixtures thereof, and such that when p is 1, Z is a member selected from the group consisting of alkylene, oxyalkylene, phenylene and oxyphenylene, and R is a member selected from the group consisting of and corresponding disiloxane and polysiloxane groups having 1 to 6 free valences, in which m in each instance corresponds in value to the number of free valences present in each said R member and in which R is a alkyl, alkenyl, phenyl, alkoxy, and phenoxy, and recovering the resultant polymeric compound.

2. Process according to claim 1 wherein said borane amine is selected from the group consisting of N-trimethylborazane, N-triethyl-borazane, N-tripropyl-borazane, N- tributyl borazane, N-diethyl-N-butyl-borazane, N-dimethyl-N-cyclohexyl-borazane, N-dimethyl-N-phenyl-borazane, pyridine-borine, N-diethyl-borazane, and N-lauryl-bora- Zane, and said thiocyanate is selected from the group consisting of methylthiocyanate, ethylthiocyanate, nand i-propylthiocyanate, n-, iand tert.-butylthiocyanate, hexylthiocyanate, octylthiocyanate, dodecylthiocyanate, hexadecylthiocyanate, octadecylthiocyanate, methoxy-methyl thiocyanate, benzylthiocyanate, 4-chloro-benzylthiocyanate, 2-fluoro-ethylthiocyanate, 2-bromo-l-methyl-propylthiocyanate, 5,5,S-trifluoro-pentylthiocyanate, 2-methyl-2- thiocyanato-butane, 3,5,5 trimethylhexyl-thiocyanate, allyl-thiocyanate, 3-chloro-allyl-thiocyanate, 3-ethyl-allylthiocyanate, oleylthiocyanate, 2-thiocyanato-butadiene- (1,3), cyclohexylthiocyanate, 4-methylcyclohexyl-thiocyanate, phenylthiocyanate, l-naphthylthiocyanate, 3-methylphenyl-thiocyanate, 4 dimethylaminophenyl-thiocyanate, 1,4-dithiocyanato-butene-(2), 2,3-dibromo-1,4-dithiocyanato-butane, bis-(2-thiocyanatoeth0xy)-methane, di-(2,2- thiocyanato-ethyl) ether, di-(4,4'-thiocyanato-n-butyl) ether, trimethyl-thiocyanato-methylsilane, ethyldimethylthiocyanate methylsilane, phenyl dimethylthiocyanatomethylsilane, methoxy-dimethyl-thiocyanato-methylsilane, ethoxy-methyl-ethyl-thiocyanato-methylsilane, phenoxydiphenyl thiocyanato-methylsilane, trimethyl-(p-thiocyanato-phenyl) silane, trimethyl-(a-thiocyanato-ethyl)-silane, trimethyl-(y-thiocyanato-propyl)-silane, his-(thio-r cyanato-methyl) -dimethylsilane, triphenyl-('y-thiocyanatopropylJ-silane, triethyl- (2-thiocyanato-ethoxy)-silane, 1-,3-

bis-(thiocyanato-methyl)-1,1,3,3 tetramethyl-disiloxane,

heptamethyl ,thiocyanato-rnethy1-cyclo-tetrasiloxane, tri-,

methyl-tris (thiocyanato methyl)-eyclo-trisiloxane, 04,0:- bis (thiocyanato-methyl)-polymethyl-polysiloxane, tris- (thiocyanato-methyl) phosphine, tris (p-thiocyanatophenyl) phosphine oxide, tris-(p-thiocyanato-phenyl)- phosphate, diethyl-thiocyanatomethyl-phosphine oxide, pthiocyanato-phenyl-phosphonic acid dimethyl ester, tris- (fi-thiocyanato-ethyl) phosphate, triphenyl ('y-thiocyanato-propyl)-tin, tripropyl- ('y-thiocyanato-propyl) -tin, di-

cyanato ethoxy)-tin, allyl thiocyanate, 2 thiocyanatoibutadiene (1,3) and allyl dimethyl thiocyanatomethylsilane.

3. Process according to claim 1 wherein said mixing is carried out with one mol of borane amine per mol of corresponding thiocyanate group present.

4. Process according to claim 1 wherein said mixing is carried out with a mixture of such thiocyanates.

1 1 5. Process according to claim 1 wherein said borane amine is N-triethylborazane.

6. Process according to claim 1 wherein said mixing is carried out under pressure.

7. Process according to claim 1 wherein said mixing is carried out in the presence of a nitrile having the formula in which R is a member selected from the group consisting of alkyl, alkenyl, cyclohexyl, phenyl, naphthyl and each such member which is substituted with a substituent selected from the group consisting of phenyl, halo, and alkyl-substituted amino, and n is an integer from 1 to 6.

8. The process according to claim 7 wherein said nitrile is selected from the group consisting of acetonitrile, propionitrile, e chloro propionitrile, {3 (N-dimethyl amino) propionitrile, butyronitrile, octane-carboxylic acid nitrile, dodecane carboxylic acid nitrile, hexanecarboxylic acid nitrile, N di (B-cyanoethyD-N-methyl amine, hexahydro benzoic acid nitrile, benzonitrile, 2- chloro benzonitrile, phenyl acetonitrile, naphthonitrile, malonic acid dinitrile, glutaric acid dinitrile, adipic acid dinitrile, 1,4- dicyano butene-Z, cyanoform, 1,1,3,3-tetracyanopropane, 1,4-dicyano-butane-(2), 1,1,2,2-teracyanoethylene, said borane amine is selected from the group consisting of N-trimethyl-borazane, N-triethyl-borazane, N-tripropyl-borazane, N-tributyl borazane, N-diethyl-N- butyl borazane, N-dimethyl-N-cyclohexyl-borazane, N- dimethyl N-phenyl-borazane, pyridine-borine, N-diethylborazane, and N-lauryl-borazane, and said thiocyanate is selected from the group consisting of methylthiocyanate, ethylthiocyanate, nand i-propylthiocyanate, n-, iand tert.-butylthiocyanate, hexylthiocyanate, octylthiocyanate, dodecylthiocyanate, hexade-cylthiocyanate, octadecylthiocyanate, methoxy methylthiocyanate, benzylthiocyanate, 4 chloro-benzylthiocyanate, 2-fiuoro-ethylthiocyanate, 2-bromo-1-Inethyl-pr0pylthi0cyanate, 5,5,5- trifluoro pentyl thiocyanate, 2-methyl-2-thiocyanatebutane, 3,5,5 trimethyl-hexyl-thiocyanate, allyl-thiocya nate, 3-chloro-allyl-thiocyanate, 3-ethyl-allyl-thiocyanate, oleylthiocyanate, 2 thiocyanato-butadiene-(1,3), cyclohexylthiocyanate, 4-methyl-cyclohexyl-thiocyanate, phenylthiocyanate, 1 naphthyl thiocyanate, B-rnethyl-phenyl thiocyanate, 4 dimethylamino-phenyl-thiocyanate, 1,4-dithiocyanato-butene-(2), 2,3-dibromo-1,4-dithiocyanato butane, bis (2-thiocyanato-ethoxy)-methane, di- (2,2 thiocyanato ethyl) ether, di-(4,4-thiocyanato-nbutyl) ether, trimethyl-thiocyanato-methylsilane, ethyldimethyl thiocyanator methylsilane, phenyl-dimethylthiocyanato methylsilane, methoxy dimethyl-thiocyanato methylsilane, ethoxy methyl-ethyl-thiocyanatomethylsilane, phenoxy diphenyl thiocyanato-methylsilane, trimethyl (p-thiocyanato-phenyl)-silane, trimethyl (or thiocyanato-ethyl)-silane, trimethyl-(w-thiocyanato propyl) silaue, bis-(thiocyanato-methyl)-dimethy-lsilane, triphenyl ('y thiocyanato-propyl)-silane, triethyl (2 thiocyanato ethoxy)-silane, 1,3-bis-(thiocyanato methyl) 1,1,3,3-tetramethyl-disiloxane, heptamethyl thiocyanato methyl cyclo-tetrasiloxane, trimethyl tris (thiocyanato methyl)-cyclotrisiloxane, a,w bis (thiocyanato methyl)-polymethyl-polysiloxane, tris (thiocyanato methyl) phosphine, tris (pthiocyanato phenyl) phosphine oxide, tris (p-thiocyanato phenyl) phosphate, diethyl-thiocyanatomethylphosphine oxide, p-thiocyanato-phenyl-phosphonic acid dimethyl ester, tris-(B-thiocyanato-ethyl)-phosphate, triphenyl ('y thiocyanatopropyl)-tin, tripropyl-( -thiocyanato propyl) tin, dibutyl-bis-('y-thiocyanato-propyl)-tin, triphenyl-(fl-thiocyanato-ethoxy)-tin, allyl-thiocyanate, Z-thiocyanato-butadiene-(1,3) and allyl-dimethyl-thiocyanatomethyl-silane.

9. Process according to claim 7 wherein said mixing is carried out with one mol of borane amine per each mol of corresponding thiocyanate and nitrile group present.

12 10. Process according to claim 7 wherein said mixing is carried out with a mixture of such thiocyanates and a mixture of such nitriles.

11. Process according to claim 7 wherein said borane amine is N-triethyl borazane.

12. Process according to claim 7 wherein said mixing is carried out under pressure.

13. Polymeric boron-nitrogen-sulfur compound produced according to claim 1.

14. Polymeric boron-nitrogen-sultur compound produced according to claim 7.

15. Polymeric boron-nitrogen-sulfur-silicon compounds having the physical constants: n =1.53O0, d =l.007, -986 cp., prepared by reacting N-triethyl borazane and ethyl-dimethyl-thiocyanatomethyksilane at about 200 C.

16. A polymeric boron-nitrogen-sulfur compound having the physical constants: n -=l.5031, d 0.980, 1 -=447 cp., obtained by reacting N-triethyl borazane and C H SC-N at about 160 C.

17. A polymeric boron-nitro'gen-sulfur compound having the physical constants: n =1.5374, (1 :1036, obtained by reacting N-triethyl-borazane with at about 160-1-80" C.

18. A polymeric boron-nitrogen-sulfur compound having a boron content of 10.8% and a sulfur content of 12.0% and a nitrogen content of 14.6%, obtained by reacting N-triethyl-borazane with n-C H SCN and adipic dinitrile at about 170-180" C. i

19. A polymeric boron-nitrogen-sulfur compound having a boron content of 10.9%, a sulfur content of 15.4% and a nitrogen content of 14.3%, obtained by reacting N-triethyl-borazane with n-C H SCN and 1.4-dicyanobutene-(Z) at about 170 C.

20. A polymeric boron-nitrogen-sulfur compound with the physical constants: n =1.5280; d =1.003',

obtained by reacting N-triethy'l-borazane with N-butylthiocyanate at about C.

21. A polymeric boron-nitrogen-sulfur-silicon compound having the physical constants. n =1.4352, d =1.005, n a=77.9 cp., obtained by reacting N-triethyl borazane with n e-bis-(thiocyanato-methyl)-poly-dimethyl-siloxane at about C.

22. A polymeric boron-nitrogen-sulfur compound having the physical constants: n =l.4675, d =1.034, n ==723 cp., obtained by reacting N-triethyl-borazane with n-C H SCN and C H CH C=N at about 140- C.

23. A polymeric boron-nitrogen-sulfur compound having the physical constants: n =1.5211, (1 :1025, 1 ==60;8 cp., obtained by reacting N-triethyl-borazane with n-C H SCN and ClCHgCHgCEN at about 150- C.

24. A polymeric boron-nitrogen-sulfur compound hav-' ing a melting point between 235 and 237 by reacting pyridine borazane with at about IDO -150 C.

25. A polymeric boron-nitrogen-sulfur compound having a melting point of 135 to 138 C., obtained by reacting N-triethyl-borazane with and'mc-mcugcri czN-j at about 130-l60 c.

C., obtained 13 26. A polymeric boron-nitrogeu-sulfur compound having the physical constant: It :1.5253, obtained by reacting N-dimethyl-N-phenyl-borazane with and 1.3 bis (thiocyanato-methyl)-1.1.3.3-tetramethyldisiloxane at about 120-140" C.

27. A polymeric boron-nitrogen-sulfur compound having the physical constants: n =1.6061, d :1.2003, n =6823 cp., obtained by reacting N-tributyl-borazane with QCHPSON, @SCN and GEN at about 140 C.

30. A polymeric boron-nitrogensu1fur silicon compound having a boron content of 2.6% and a sulfur content of 5.3% and a nitrogen content of 2.4% and a silicon content of 33.2%, obtained by reacting N-triethylborazane with a polymethyl-siloxane substituted by thiocyanato-methyl groups having the proximate composition 38Si(CH 0.l4(NCSCH )Si(CH )0.2(CH SiO at about 135-140 C.

References Cited UNITED STATES PATENTS 3,238,152 3/1966 Horn 260-784 FOREIGN PATENTS 1,000,425 8/ 1965 Great Britain.

DONALD E. CZAJA, Primary Examiner. L. J. BERCOVITZ, Examiner.

M. I. MARQUIS, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,357,949 December 12, 1967 Elmar-Manfred Horn et al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, lines 61 and 64, for "p-thiocayanto", each occurrence, read p-thiocyanato column 4, line 33, for "borazene" read borazane line 38, for "or" read of columns 7 and 8, TABLE 3, opposite EX. 13, second column, for "S0.6g.=0.4 mol." read 59.6g.=0.4 mol. column 11, line 50, for "thiocyanator" read thiocyanato column 14, line 10, for "proximate" read opproximate Signed and sealed this 22nd day of April 1969.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. PROCESS FOR THE PRODUCTION OF POLYMERIC ORGANIC BORON-NITROGEN-SULFUR COMPOUNDS WHICH COMPRISES MIXING AT A TEMPERATURE BETWEEN ABOUT 0-600*C. BORANE AMINE HAVING THE FORMULA
 7. PROCESS ACCORDING TO CLAIM 1 WHEREIN SAID MIXING IS CARRIED OUT IN THE PRESENCE OF A NITRILE HAVING THE FORMULA
 13. POLYMERIC BORON-NITROGEN-SULFUR COMPOUND PRODUCED ACCORDING TO CLAIM
 1. 14. POLYMERIC BORON-NITROGEN-SULFUR COMPOUND PRODUCED ACCORDING TO CLAIM
 7. 